Process of hydrocyanation of unsaturated carboxylic acid derivatives

ABSTRACT

The present invention is directed to compositions of specific carboxylic acid, fatty acid or oil derivatives containing nitrile groups and methods of their preparation. The preparation involves a hydrocyanation reaction. A method of hydrgenating the nitrile containing carboxylic acid acids obtained by above hydrocyanation to produce amine containing carbixylic acids is also disclosed in this invention.

FIELD OF THE INVENTION

This invention is related to the field of hydrocyanation of olefins andin particular, hydrocyanation of unsaturated carboxylic acids, fattyacids and oils comprising these acids.

BACKGROUND OF THE INVENTION

Unsaturated fatty acids and oils comprising unsaturated carboxylic acidsare attractive substrates for a variety of applications such as monomersfor polymeric materials, as ingredients in composites, as lubricants oras fine chemicals. These materials are especially attractive since theyare based on natural sources and therefore offer an environmentally andecologically responsible route to useful chemicals. Significant efforthas been devoted toward further transformations of these long chainunsaturated fatty acids to arrive at new, functional materials.

Towards this end the current invention provides a process ofhydrocyanation of unsaturated and/or poly-unsaturated carboxylic acids,especially fatty acids and/or oils comprising these fatty acids to formthe corresponding fatty acid/oil nitrile products. In case of the oils,typical examples are natural occurring oils, for example soybean oil.The products can be mononitriles, dinitriles and/or polynitriles.Furthermore these nitriles can be converted to the correspondingmethylene-amines via a hydrogenation reaction.

Unsaturated carboxylic acids, and especially fatty acids and theirderivatives containing nitrile groups are of interest as lubricants,surfactants or precursors to a variety of useful molecules. Typicalexamples of unsaturated fatty acids, which are naturally occurring,include mono- or polyunsaturated carboxylic acids, such as oleic acid,lauroleic acid, myristoleic acid, palmitoleic acid, linoleic acid, andarachidonic acid. Naturally occurring oils, for example soybean oil,comprise glycerin esters of these unsaturated fatty acids. Other typicaluseful unsaturated carboxylic acids are, for example, 3-pentenoic acidor 4-pentenoic acid.

Goertz et al. in Chem. Commun., 1521 (1997) disclosed a hydrocyanationreaction of ω-unsaturated fatty acid esters (i.e. containing a terminalolefin) using nickel phosphine catalysts. The reported yields areundesirable for commercial application. Additionally, it is known in theart that internal olefins, such as those in many naturally occurringfatty acids and esters, are more difficult to react in a hydrocyanationprocess than terminal olefins, such as those found in ω-unsaturatedfatty acid esters.

WO 99 06358 A1 disclosed the hydrocyanation of mono-ethylenicallyunsaturated ester compounds to provide linear terminal nitrile moleculesbut did not disclose the hydrocyanation of carboxylic acids. Acidiccompounds are known to deactivate catalysts and degrade typicalhydrocyanation ligands.

Prior to the present invention, it was not known that unsaturated fattyacids or naturally occurring oils with olefinic unsaturation could beconverted selectively in a hydrocyanation process to the correspondingfatty acid derivatives with nitrile groups in high yields. It was alsonot known that the so formed derivatives of fatty acids containingnitrile groups could be converted selectively in a hydrogenation processto the fatty acid derivatives with the corresponding amine groups. Thereis a need to access fatty acid derivatives, which have one or moreadditional functional groups, such as nitriles, amines, alcohols orcarboxylic acids. In particular, derivatives of plant oils like soybeanoil, which contain one or more additional functional groups are ofinterest.

Therefore, there remains a need for specific nitrile derivatives ofunsaturated carboxylic acids, especially unsaturated fatty acids and/oroils of unsaturated fatty acids and a method to produce these compoundsin general. There is also a need for derivatives of unsaturated fattyacids, which contain amine groups and for a method to produce suchderivatives, which contain amine groups. These needs are met by thepresent invention.

SUMMARY OF THE INVENTION

The present invention is directed to compositions of specific carboxylicacid, fatty acid or oil derivatives containing nitrile groups andmethods of their preparation. The preparation involves a hydrocyanationreaction. A method of hydrogenating the nitrile containing carboxylicacid acids obtained by above hydrocyanation to produce amine containingcarboxylic acids is also disclosed in this invention.

The present invention is, therefore, a composition of matter ofstructural formula III:

and a composition of matter of structural formula V:

wherein:

each A is independently a group comprising one or more hydrocarbonfragments comprising —(CH₂)_(w)—, alkene containing fragments comprising—CH═CH—, or nitrile containing fragment comprising —(CH₂CHCN)— or—(CH(CN)CH₂)—, or a combination of two or more of these fragments in anyorder;

each B is independently A′-H, wherein A′ is a group comprising one ormore hydrocarbon fragment comprising —(CH₂)_(w)—, alkene containingfragment comprising —CH═CH—, or a nitrile containing fragment comprising—(CH₂CHCN)— or —(CH(CN)CH₂)—, or a combination of two or more of thesefragments in any order; and

wherein, w is independently 0 or a positive integer, preferably between0 and 20.

Also disclosed is a hydrocyanation process, said process comprisingconverting a starting carboxylic acid in the presence of a catalyst toproduce a derivative of carboxylic acid comprising one or more compoundsof formula (I):

wherein:

A is a group comprising one or more hydrocarbon fragments comprising—(CH₂)_(w)—, alkene containing fragments comprising —CH═CH—, or nitrilecontaining fragment comprisings —(CH₂CHCN)— or —(CH(CN)CH₂)—, or acombination of two or more of these fragments in any order;

B is A′-H, wherein A′ is group comprising one or more hydrocarbonfragment comprising —(CH₂)_(w)—, alkene containing fragment comprising—CH═CH—, or a nitrile containing fragment comprising —(CH₂CHCN)— or—(CH(CN)CH₂)—, or a combination of two or more of these fragments in anyorder; and

R is H or a glycerol derivative; and

wherein, w is 0 or a positive integer, preferably between 0 and 20.

Also disclosed is a process of hydrogenation comprising hydrogenatingthe carboxylic acid derivative to produce acid amine compounds ofstructural formula (II):

wherein

C is a group comprising one or more hydrocarbon fragments comprising—(CH₂)_(x)—, alkene containing fragments comprising —CH═CH—, nitrilecontaining fragments comprising —(CH₂CHCN)— or —(CH(CN)CH₂)—, or aminecontaining fragments comprising —(CH₂CH(CH₂NH₂)— or —(CH(CH₂NH₂)CH₂)—,or a combination of one or more of these fragments in any order;

D is H or C′—H wherein C′ is a group comprising one or more hydrocarbonfragments comprising —(CH₂)_(x)—, alkene containing fragments comprising—CH═CH—, nitrile containing fragments comprising —(CH₂CHCN)— or—(CH(CN)CH₂)—, or amine containing fragments comprising —(CH₂CH(CH₂NH₂)—or —(CH(CH₂NH₂)CH₂)—, or a combination of two or more of these fragmentsin any order;

R is H or a glycerol derivative; and

x is 0 or a positive integer, preferably between 0 and 20, wherein x isindependently chosen each time it is utilized in the structure.

Notable for this invention is the use of oleic acid as the substrate toprovide a nitrile derivative or a mixture of nitrile derivatives. Whilethis invention may provide a variety of isomers described by (I), theprocess shows preference for the terminal nitrile, (III):

Additionally, notable is amine derivative (IV) of correspondingstructure.

Glycerol tri-esters with olefinic unsaturation, comprising naturallyoccurring plant and/or animal oils, are important feedstocks within thescope of the present invention. These glycerol tri-esters may beconstructed of fatty acid fragments. Products derived from themaccording to the present invention can be described by formula (V)and/or (VI):

wherein, A, B, C and D are defined as above and are of independentidentity each time utilized in the structure.

These compounds are useful as organic synthesis precursors or aslubricants or in surfactant applications.

Natural glyceridic oils may also contain different degrees ofunsaturation, which deviate from the stoichiometry suggested by theoleic acid derivative. Other oils useful for this invention includeunsaturated plant oils such as tung oil, mono-, di-, and tri-glycerideoils such as oils from soybeans, oil seed rape, linseed, olive oil,castor oil, mustard seed oil, ground nut oil, coconut oil, corn oil,cottonseed oil, palm oil, peanut oil, safflower oil and phenolic oilssuch as cashew nut shell liquid.

Accordingly, it is one object of the present invention to providecarboxylic acid derivatives and especially fatty acid or oil derivativescontaining nitrile groups, as well as a process for preparing them andtheir corresponding amines. It is another object of the presentinvention to provide a method for preparing such unsaturated fatty acidor oil derivatives. These and other objects will become apparent in thefollowing detailed description.

DETAILED DESCRIPTION OF THE INVENTION

Carboxylic acids comprising one or more of the compounds of formula (I):

are obtained by hydrocyanation of unsaturated carboxylic acids wherein:

A is a group comprising one or more hydrocarbon fragments comprising—(CH₂)_(w)—, alkene containing fragments comprising —CH═CH—, or nitrilecontaining fragment comprisings —(CH₂CHCN)— or —(CH(CN)CH₂)—, or acombination of two or more of these fragments in any order;

B is A′-H, wherein A′ is group comprising one or more hydrocarbonfragment comprising —(CH₂)_(w)—, alkene containing fragment comprising—CH═CH—, or a nitrile containing fragment comprising —(CH₂CHCN)— or—(CH(CN)CH₂)—, or a combination of two or more of these fragments in anyorder; and

R is H or a glycerol derivative; and

wherein, w is 0 or a positive integer, preferably between 0 and 20.

These carboxylic acid derivatives, especially these fatty acid or oilderivatives containing nitrile groups, either alone, mixtures of these,and/or isomers of these, are also useful as precursors for other usefulmolecules. For instance, a carboxylic acid comprising one or morecompounds of formula (I) can be converted in a hydrogenation reaction tothe corresponding amines comprising one or more compounds of the formula(II):

wherein

C is a group comprising one or more hydrocarbon fragments comprising—(CH₂)_(x)—, alkene containing fragments comprising —CH═CH—, nitrilecontaining fragments comprising —(CH₂CHCN)— or —(CH(CN)CH₂)—, or aminecontaining fragments comprising —(CH₂CH(CH₂NH₂)— or —(CH(CH₂NH₂)CH₂)—,or a combination of one or more of these fragments in any order;

D is H or C′—H wherein C′ is a group comprising one or more hydrocarbonfragments comprising —(CH₂)_(x)—, alkene containing fragments comprising—CH═CH—, nitrile containing fragments comprising —(CH₂CHCN)— or—(CH(CN)CH₂)—, or amine containing fragments comprising —(CH₂CH(CH₂NH₂)—or —(CH(CH₂NH₂)CH₂)—, or a combination of two or more of these fragmentsin any order;

R is H or a glycerol derivative; and

x is 0 or a positive integer, preferably between 0 and 20, wherein x isindependently chosen each time it is utilized in the structure.

Notable for this invention is the use of oleic acid as the substrate toprovide a nitrile derivative or a mixture of nitrile derivatives. Whilethis invention may provide a variety of isomers described by (I), theprocess shows preference for the terminal nitrile, (III).

Additionally, notable is amine derivative (IV) of correspondingstructure.

The product is provided as a single compound or mixtures of isomers,described by (II).

Additionally, notable is the use of linoleic acid as the substrate toprovide a product comprising nitrile derivatives (VII)-(VIII), and/orthe amine derivatives of corresponding structure (VII-A) and (VIII-A).The products are provided as single compounds, mixtures of compoundsand/or mixtures of isomers.

Glycerol tri-esters with olefinic unsaturation, comprising naturallyoccurring plant and/or animal oils, are important feedstocks within thescope of the present invention. These glycerol tri-esters may beconstructed of fatty acid fragments. Products derived from themaccording to the present invention can be described by formula (V)and/or (VI):

wherein, A, B, C and D are defined as above and are of independentidentity each time utilized in the structure.

These compounds are useful as organic synthesis precursors or aslubricants or in surfactant applications.

Natural glyceridic oils may also contain different degrees ofunsaturation, which deviate from the stochiometry suggested by the oleicacid derivative. Other oils useful for this invention includeunsaturated plant oils such as tung oil, mono, di, and tri-glycerideoils such as oils from soybeans, oil seed rape, linseed, olive oil,castor oil, mustard seed oil, ground nut oil, coconut oil, corn oil,cottonseed oil, palm oil, peanut oil, safflower oil and phenolic oilssuch as cashew nut shell liquid.

The inventors have discovered that unsaturated carboxylic acids,especially unsaturated fatty acids and/or oils of fatty acids can becontacted with hydrogen cyanide, in the presence of a catalyst andoptionally a promoter at a temperature of about 0° C. to about 120° C.to yield carboxylic acid derivatives of the formula (I), wherein thecatalyst comprises a transition metal, preferentially nickel and anorganic phosphorous ligand. Further, they have discovered that compoundsor mixtures described by (I) (and thus (III) and (V)) may be convertedto compounds or mixtures described by (II) (and thus (IV) and (VI)) bycontacting compounds or mixtures (I) with hydrogen, in the presence of atransition metal catalyst at a temperature in the range of about 50° C.to about 180° C. and a pressure in the range of of about 50 to about5000 psig (340 to 34,480 kPa), optionally in the presence of a solvent.A simple extension of this process would encompass the use of simplefatty acid esters as the starting material, instead of fatty acids. Suchfatty acid esters can be prepared via the reaction of alcohols withfatty acid oils and comprise alkyl and aryl esters. Examples of fattyacid esters include methyl oleate, methyl linoleate, ethyl oleate, butyloleate and the like.

Thus, in one embodiment, the present invention provides a hydrocyanationmethod for preparing derivatives of unsaturated carboxylic acids,especially fatty acids and/or oils, which contain nitrile groups.Generally, the present method yields the acid derivative as a mixture ofisomers. The mixture obtained by the present method generally does notcontain the isomers in equal amounts. Instead, the method may yield oneor several compounds as main products, while others are formed asby-products in varying amounts. The method can be implemented to favorone set of compounds as the main products. The set of compounds favoredin this method is a function of process conditions and/or the type ofcatalyst or catalysts used and/or the type of ligand used in thehydrocyanation reaction and/or the use of an optional promoter in thehydrocyanation reaction. However, it is to be understood that both theindividual compounds and also the mixtures thereof are within the scopeof the present invention.

The method for making the compounds of the present invention involves ahydrocyanation process with the use of a ligand and a Group VIII metalor compound. Optionally, one may use a Lewis acid in the process as apromoter, and one may optionally use a solvent.

Generally, a Group VIII metal or compound thereof is combined with atleast one ligand to provide the catalyst. Among the Group VIII metals orcompounds, nickel, cobalt, and palladium compounds are preferred to makethe hydrocyanation catalysts. A nickel compound is more preferred. Azero-valent nickel compound that contains a ligand that can be displacedby a ligand of the prior art is the most preferred source of Group VIIImetal or Group VIII metal compound.

Zero-valent nickel compounds can be prepared or generated according tomethods known in the art. Three preferred zero-valent nickel compoundsare Ni(COD)₂ (COD is 1,5-cyclooctadiene), Ni(P(o-OC₆H₄CH₃)₃)₃ andNi{P(O-o-C₆H₄CH₃)₃}₂(C₂H₄); these are known in the art.

Alternatively, divalent nickel compounds can be combined with a reducingagent, to serve as a source of zero-valent nickel in the reaction.Suitable divalent nickel compounds include compounds of the formula NiX²₂ wherein X² is halide, carboxylate, or acetylacetonate. Suitablereducing agents include metal borohydrides, metal aluminum hydrides,metal alkyls, Li, Na, K, Zn, Al or H₂. Elemental nickel, preferablynickel powder, when combined with a halogenated catalyst is also asuitable source of zero-valent nickel.

Suitable ligands for the present invention contain trivalent phosphorusatoms in which each trivalent phosphorous atom is known as phosphite orphosphinite. The ligands useful in the present invention can bebidentate ligands meaning that two trivalent phosphorus atoms in themolecule are each bonded to the same organic group, which bridges thetrivalent phosphorus atoms together. The ligands in the presentinvention can also be multidentate with a number of phosphorous atoms inexcess of 2 or of polymeric nature in which the ligand/catalystcomposition is not homogeneously dissolved in the process mixture.Monodentate ligands, may be used in place of the ligands of thisinvention, but they provide low conversion to the desired products andsuffer from poor rate and productivity. Their performance isinsufficient for commercial applications. The preferred ligands in thisinvention are bidentate phosphite ligands.

Suitable bidentate phosphites are of the type disclosed in U.S. Pat.Nos. 5,512,695; 5,512,696; 5,663,369; 5,688,986; 5,723,641; 5,959,135;6,120,700; 6,171,996; 6,171,997; 6,399,534, hereby incorporated byreference. Suitable bidentate phosphinites are of the type disclosed inU.S. Pat. Nos. 5,523,453 and 5,693,843, hereby incorporated byreference.

The preferred bidentate phosphite ligands are of the followingstructural formulae:(R¹O)₂P(OZO)P(OR¹)₂,  (XI)

In formulae XI, XII and XIII, R¹ is phenyl, unsubstituted or substitutedwith one or more C₁ to C₁₂ alkyl or C₁ to C₁₂ alkoxy groups; ornaphthyl, unsubstituted or substituted with one or more C₁ to C₁₂ alkylor C₁ to C₁₂ alkoxy groups; and Z and Z¹ are independently selected fromthe group consisting of structural formulae XIV, XV, XVI, XVII, andXVIII

wherein:

R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, and R⁹ are independently selected from H, C₁to C₁₂ alkyl, and C₁ to C₁₂ alkoxy;

W is O, S, or CH(R¹⁰); and

R¹⁰ is H or C₁ to C₁₂ alkyl.

wherein:

R¹¹ and R¹² are independently selected from H, C₁ to C₁₂ alkyl, and C₁to C₁₂ alkoxy; and CO₂R¹³;

R¹³ is C₁ to C₁₂ alkyl or C₆ to C₁₀ aryl, unsubstituted or substitutedwith C₁ to C₄ alkyl;

Y is O, S, CH(R¹⁴); and

R¹⁴ is H or C₁ to C₁₂ alkyl.

wherein:

R¹⁵ is selected from H, C₁, to C₁₂ alkyl, and C₁ to C₁₂ alkoxy; andCO₂R¹⁶; and

R¹⁶ is C₁ to C₁₂ alkyl or C₆ to C₁₀ aryl, unsubstituted or substitutedwith C₁ to C₄ alkyl.

In the structural formulae X through XVIII, the C₁ to C₁₂ alkyl, and C₁to C₁₂ alkoxy groups may be straight chains or branched.

The ratio of ligand to active nickel can vary from a ligand to nickelratio of about 0.5:1 to a ligand to nickel ratio of about 100:1.Preferentially the ligand to nickel ratio ranges from about 1:1 to about4:1.

Preferably, the process of this invention is carried out in the presenceof one or more Lewis acid promoters that affect both the activity andthe selectivity of the catalyst system. The promoter may be an inorganicor organometallic compound in which the cation is selected fromscandium, titanium, vanadium, chromium, manganese, iron, cobalt, copper,zinc, boron, aluminum, yttrium, zirconium, niobium, molybdenum, cadmium,rhenium and tin. Examples include but are not limited to ZnBr₂, Znl₂,ZnCl₂, ZnSO₄, CuCl₂, CuCl, Cu(O₃SCF₃)₂, CoCl₂, Col₂, Fel₂, FeCl₃, FeCl₂,FeCl₂(THF)₂, TiCl₄(THF)₂, Cl₂Ti(OiPr)₂, MnCl₂, ScCl₃, AlCl₃,(C₈H₁₇)AlCl₂, (C₈H₁₇)₂AlCl, (iso-C₄H₉)₂AlCl, Ph₂AlCl, PhAlCl₂, ReCl₅,ZrCl₄, NbCl₅, VCl₃, CrCl₂, MoCl₅, YCl₃, CdCl₂, LaCl₃, Er(O₃SCF₃)₃,Yb(O₂CCF₃)₃, SmCl₃, B(C₆H₅)₃, R⁴⁰Sn(O₃SCF₃) where R⁴⁰ is an alkyl oraryl group. Preferred promoters include FeCl₂, ZnCl₂, CoCl₂, Col₂,AlCl₃, B(C₆H₅)₃, and (C₆H₅)₃Sn(O₃SCF₃). The mole ratio of promoter toGroup VIII transition metal present in the reaction can be within therange of about 1:16 to about 50:1, with 0.5:1 to about 2:1 beingpreferred.

The ligand compositions of the present invention may be used to formcatalysts, which may be used for the hydrocyanation of unsaturatedcarboxylic acids, especially fatty acids or esters with or without aLewis acid promoter.

The process comprises contacting, in the presence of the catalyst, anunsaturated carboxylic acid or oil or mixtures of one or more of thesewith a hydrogen cyanide-containing fluid under conditions sufficient toproduce a nitrile. Any fluid containing about 1 to 100% HCN can be used.Pure hydrogen cyanide may be used.

The hydrocyanation process can be carried out, for example, by charginga suitable vessel, such as a reactor, with an unsaturated fatty acid oroil, or mixtures of one or more of these, catalyst and optionallysolvent, to form a reaction mixture. Hydrogen cyanide can be initiallycombined with other components to form the mixture. However, it ispreferred that HCN be added slowly to the mixture after other componentshave been combined. Hydrogen cyanide can be delivered as a liquid or asa vapor to the reaction. As an alternative, a cyanohydrin can be used asthe source of HCN as known in the art.

Another suitable technique is to charge the vessel with the catalystand, optionally, solvent and feed both the unsaturated carboxylic acid,the fatty acid or oil and the HCN slowly to the reaction mixture.

The molar ratio of unsaturated carboxylic acid/ester to catalyst can bevaried from about 10:1 to about 10,000:1. The molar ratio ofHCN:catalyst can be varied from about 5:1 to about 10,000:1. The processcan be run in continuous or batch mode.

Preferably, the reaction mixture is agitated, for example, by stirringor shaking. The present compounds can be individually isolated from thereaction mixture, using known conventional methods, such aschromatography or fractional distillation or crystallization.

The hydrocyanation can be carried out with or without a solvent. Thesolvent, if used, can be liquid at the reaction temperature and pressureand inert towards the unsaturated carboxylic acid/oil and the catalyst.Examples of suitable solvents include hydrocarbons such as benzene,xylene, toluene or combinations thereof; ethers such as tetrahydrofuran(THF), nitriles such as acetonitrile, adiponitrile, or combinations oftwo or more thereof.

The exact temperature is dependent to a certain extent on the particularcatalyst being used, and the desired reaction rate. Normally,temperatures in the range of from about 0° C. to about 200° C. can beused, the range of about 25° C. to about 120° C. being preferred.

The process can be run at atmospheric pressure. Pressures of from about50.6 to about 1013 kPa are preferred. Higher pressures, up to 10,000 kPaor more, can be used, if desired.

The time required can be in the range of from a few seconds to manyhours (such as 2 seconds to 72 hours), depending on the particularconditions and method of operation.

The present unsaturated carboxylic acid derivatives containing nitrilegroups can be used alone or in mixtures with one another, for furtherfunctionalization. For example, they can be converted to theircorresponding amines by hydrogenation. Thus the nitrile products eitheralone or as mixtures of isomers may be contacted with hydrogen in thepresence of a catalyst, optionally in the presence of a solvent to yieldamine compounds.

During the hydrogenation process the feed (i.e. compounds described by(I) either alone or in mixtures of isomers) is contacted with hydrogen.The mole ratio of hydrogen to feed is not critical as long as sufficienthydrogen is present to produce the desired derivatives described by(II). Hydrogen is preferably used in excess. Hydrogen pressures aregenerally in the range of about 340 kPa (˜50 psig) to about 34,480 kPa(˜5000 psig), with about 1480 to about 7000 kPa preferred. Thehydrogenation process can be conducted at temperatures from about 50° C.to about 180° C., preferably from about 65° C. to about 100° C.

Preferred catalysts for hydrogenating nitriles to amines comprise one ormore elements from the series of transition metals, particularly usefulare iron, cobalt, nickel, rhodium and combinations thereof. Thehydrogenation catalyst may also comprise one or more elements inaddition to the transition metals mentioned above, for example, elementsof Group IA (including lithium, sodium and potassium), elements of GroupIIA (including magnesium and calcium), titanium, elements of Group VI(including chromium, molybdenum and tungsten), elements of Group VIII(including palladium) and/or aluminum, silicon, boron and/orphosphorous. The hydrogenation catalyst can also be in the form of analloy, including a solid solution of two or more elements.

The transition metal for hydrogenation can also be supported on aninorganic support such as alumina, magnesium oxide and combinationsthereof. The metal can be supported on an inorganic support by any meansknown to one skilled in the art such as, for example, impregnation,co-precipitation, ion exchange, or combinations of two or more thereof.The metal can be reduced before the hydrogenation reaction by any meansknown to one skilled in the art such as, for example, pretreatment withhydrogen, formaldehyde or hydrazine.

The hydrogenation catalyst can be present in any appropriate physicalshape or form. It can be in fluidizable forms, powders, extrudates,tablets, spheres or combinations of two or more thereof. Thehydrogenation catalyst may be in sponge metal form, for example, theRaney® nickels and Raney® cobalts. The molar ratio of hydrogenationcatalyst to feed can be any ratio as long as the ratio can catalyze thehydrogenation. The weight ratio of hydrogenation catalyst to feed isgenerally in the range of from about 0.0001:1 to about 1:1, preferablyabout 0.001:1 to about 0.5:1. If the catalytic element is supported onan inorganic support or is a portion of an alloy or solid solution, thecatalytic element is generally present in the range of from about 0.1 toabout 60, preferably about 1 to about 50, and most preferably about 2 toabout 50 weight percent based on the total hydrogenation catalystweight.

It will be appreciated that one skilled in the art will select thecatalyst to optimize the rate of reaction, selectivity of reaction andthe level of catalyst leaching. The preferred nitrile hydrogenationcatalyst is a sponge metal type catalyst. The metallic component isiron, ruthenium, cobalt, nickel or combinations thereof. Commerciallyavailable catalysts of this type are promoted or un-promoted Raney® Nior Raney® Co catalysts that can be obtained from W.R. Grace and Co.(Chattanooga, Tenn.), or alternative sponge metal catalysts available,for example, from Activated Metals Corporation (Sevierville, Tenn.) orDegussa (Parsippany, N.J.). A supported ruthenium catalyst may also beused.

The hydrogenation can optionally be conducted in the presence of asolvent. Suitable solvents include those known in the art as useful forhydrogenation reactions. Examples of these are amines, aliphaticalcohols, aromatic compounds, ethers, esters (including lactones), andamides (including lactams). Specific examples of solvents include:ammonia, toluene, tetrahydrofuran, methanol, ethanol, any isomericpropanol, any isomeric butanol and water. Preferred solvents includeammonia, and toluene. It will be appreciated that the solvent may serveto reduce the viscosity of the system to improve fluidity of thecatalyst in the reaction vessel, as well as serve to remove the heat ofreaction from the feed and products. The solvent may be present in arange of about 1% to about 75% by weight of the total reaction mixture,excluding the catalyst, preferably from about 10% to about 50%.

Optionally, a promoter may be used in the hydrogenation process to alterthe rate of the reaction and/or alter the selectivity of the reaction.Suitable promoters include water, alkali or alkaline earth metalhydroxides, quaternary ammonium hydroxides, quaternary ammoniumcyanides, quaternary ammonium fluorides, and combinations of these.Promoters may be present at from about 10 ppm to about 3% by weight ofthe total reaction mixture, excluding the catalyst, preferably fromabout 50 ppm to about 1.5%.

Having generally described this invention, a further understanding canbe obtained by reference to certain specific examples, which areprovided herein for purpose of illustration only and are not intended tobe limiting.

EXAMPLES Example 1-4 Hydrocyanation of Oleic Acid

A solution of catalyst was prepared by combining Ni(COD)₂ in toluenewith a bidentate phosphite ligand in a ratio of Ni:ligand of 1:1.1. Thissolution was sampled into a reaction vessel. Oleic acid was added to thereaction vessel, the mole ratio of oleic acid to catalyst was 50:1. Asolution of promoter was prepared by adding ZnCl₂ to acetonitrile. Thispromoter solution was added to the reaction mixture adjusting a moleratio of Ni to Zn of 1:1. Hydrogen cyanide was added to the reactionvessel via vapor feed. The hydrogen cyanide reservoir was at roomtemperature while the reaction vessel was maintained at 50° C. The vaporfeed was maintained for 24 hours after which time the samples wereanalyzed using standard GC methodology for products. The samples werefirst derivatized for analysis with a commercial reagent followingestablished procedures (BSTFA, bistrimethylsilyltrifluoroacetamide, fortypical use see for example Takao, Yuji et al. in Journal of HealthScience (2003), 49(1), 88-90). All products were analyzed by GC-MS andNMR spectroscopy. Linearity is defined by the ratio of concentrations ofthe linear acid nitrile product to the sum of all acid nitrile products.

Con- Line- version arity Entry Ligand [%] [%] 1

33 73 2

52 75 3

34 68 4

31 63

Example 5 Hydrocyanation of Soy Bean Oil

In a 100 mL flask soy bean oil (30 g) was mixed with a toluene (16 g)solution of Ni(COD)₂ (0.31 g) and the following ligand (1.03 g):

To this was added ZnCl₂ (0.045 g). A solution of hydrogen cyanide (2.85g) in tulene (11.4 g) was prepared and added to the above mixture usinga syringe pump. A feed rate of about 0.5 mL/hour was maintained at 70°C. The product composition was analyzed using LC-MS analysis on a ZorbaxRX-C18 column (150×2.1, 5 μm) after the reaction was terminated: 70.1%conversion of soy bean oil to a mixture of products with 55% of MW=911(addition of one equivalent of HCN), 35% MW=938 (addition of twoequivalents of HCN) and 10% MW=965 (addition of three equivalents ofHCN).

Example 6 Hydrogenation of Soybean Oil Nitrile

A solution of approximately 30 g of nitrile derived from soybean oil(comprising compound V) and 170 mL of toluene was prepared. The solutionwas charged to a 300 cc stirred pressure reactor with 3 g Raney® Co 2724and 4.5 g water. The vessel was purged with hydrogen and then chargedwith hydrogen and heated to 75° C. at which point the pressure wasadjusted to approximately 500 psig (3447 kPa) with hydrogen. Thereaction proceeded for ten hours during which hydrogen was constantlyreplenished to maintain the operating pressure. The hydrogen was ventedand the product recovered. Infrared and nuclear magnetic spectra of theproduct were consistent with the formation of the amine product(comprising compound VI) (IR: N—H 3350 cm⁻¹, C═O 1742 cm⁻¹).

Example 7 Hydrogenation of Oleic Acid Nitrile

To a 100 mL stirred pressure vessel were added 4.5 g of oleic acidderived nitrile (comprising compound (III) and isomers), 20 gtetrahydrofuran, 0.3 g Raney® Co 2724 and 0.3 g water. The vessel waspurged with hydrogen and 21 g anhydrous ammonia was added. The vesselwas then charged with hydrogen and heated to 100° C. at which point thepressure was adjusted to approximately 900 psig (6205 kPa) withhydrogen. The reaction proceeded for 335 minutes during which hydrogenwas constantly replenished to maintain the operating pressure. Thehydrogen and ammonia were vented and the product recovered. The productwas sparingly soluble in common solvents such as tetrahydrofuran.Infrared and nuclear magnetic spectra of the product were consistentwith the formation of the amine (IV). A probe mass spectrum furtherconfirmed the identity of the desired product (mass 313.298).

Example 8 Hydrocyanation of Linoleic Acid

In a 500 mL flask linoleic acid (25 g, 0.09 mol) was mixed with atoluene (5 g) solution of Ni(COD)₂ (0.16 g, 0.6 mmol) and the followingligand (0.61 g, 0.8 mmol).

To this was added a solution of ZnCl₂ (0.09 g, 0.65 mmol) inacetonitrile (5 g). A solution of hydrogen cyanide (4.3 g, 0.16 mol) inacetonitrile (6.5 g) was prepared and added to the above mixture using asyringe pump. After a reaction time of 26 hours at 50° C. a conversionof 87% of linoleic acid to nitrile products was achieved. By GC (BSTFAmethod) a product mixture of 90% linoleic acid nitrile and 10% linoleicacid dinitrile was observed.

Example 9 Hydrogenation of Linoleic Acid Nitrile

To a 100 mL stirred pressure vessel were added 2.7 g of linoleic acidderived nitriles (comprising compound (VII) and isomers), 20 gtetrahydrofuran, 0.5 g Raney® Co 2724 and 1 g water. The vessel waspurged with hydrogen and 20 g anhydrous ammonia were added. The vesselwas then charged with hydrogen and heated to 85° C. at which point thepressure was adjusted to approximately 900 psig (6205 kPa) withhydrogen. The reactor conditions were maintained for 360 minutes, thougha shorter time may have been sufficient. The hydrogen and ammonia werevented and the product recovered. A portion of the product was treatedwith excess bis(trimethylsilyl)trifluoroacetamide (BSTFA). Gaschromatography showed a major product peak accounting for 86% yield. Amass spectrum of the major peak from the product was consistent withformation of the amine (VII-A) (m/z=455, product plus two derivatizingtrimethylsilyl groups).

Example 10 Hydrocyanation of 3-Pentenoic Acid

In a 500 mL flask 3-pentenoic acid (10 g, 0.1 mol) was mixed with atoluene (5 g) solution of Ni(COD)₂ (0.275 g, 1 mmol) and the followingligand (1.14 g, 1.35 mmol).

To this was added a solution of ZnCl₂ (0.15 g, 1.1 mmol) in acetonitrile(5 ml). A solution of hydrogen cyanide (5.4 g, 0.2 mol) in acetonitrile(8.1 g) was prepared and added to the above mixture using a syringepump. The reaction mixture was maintained at 50° C. and the additionstopped after 18 hours. The product was analyzed after derivatizationusing BSTFA and a 50% conversion to cyano-pentanoic acid was observed.

Example 11-13 and Comparative Example 14 Hydrocyanation of 3-PentenoicAcid

A solution of catalyst was prepared by combining Ni(COD)₂ in toluenewith the phosphite ligand in a ratio of Ni:ligand of 1:1.1 if abidentate ligand was used and in a ratio of Ni:ligand of 1:4.5 if amonodentate ligand was used. This solution was sampled into a reactionvessel. 3-Pentenoic acid was added to the reaction vessel, the ratio of3-penteneoic acid to catalyst was 50:1. A solution of promoter wasprepared by adding ZnCl₂ to acetonitrile, this promoter solution wasadded to the reaction mixture with a mole ratio of Ni to Zn of 1:1.Hydrogen cyanide was added to the reaction vessel by vapor feed ofevaporating liquid hydrogen cyanide connected via feed tube to thereaction vessel. The hydrogen cyanide reservoir was at room temperaturewhile the reaction vessel was maintained at 50° C. The vapor feed wasmaintained for 24 hours after which time the samples were analyzed usingstandard GC methodology. The samples were first derivatized for analysiswith a commercial reagent following established procedures (BSTFA,bistrimethylsilyltrifluoroacetamide, for typical use see for exampleTakao, Yuji et al. in Journal of Health Science (2003), 49(1), 88-90).The products were analyzed by GC-MS and NMR spectroscopy. Linearity isdefined as the ratio of concentrations of the 5-cyano-pentanoic acidisomer to the sum of all cyano-pentanoic acid isomers.

Conversion Linearity Example Ligand [%] [%] 11

76 93 12

85 92 13

79 91 C. ex 14

no conversion

Various modifications, alterations, additions or substitutions of theprocess and compositions of this invention will be apparent to thoseskilled in the art without departing from the spirit and scope of thisinvention. This invention is not limited to the illustrative embodimentsset forth herein, but rather is defined by the following claims.

1. A compound of formula III: